Phenyl-pyta-tricarbonylrhenium(I) complexes: combining a simplified structure and steric hindrance to modulate the photoluminescence properties,Dalton Transactions

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Phenyl-pyta-tricarbonylrhenium(I) complexes: combining a simplified structure and steric hindrance to modulate the photoluminescence properties
Dalton Transactions ( IF 3.5 ) Pub Date : 2021-09-15 , DOI: 10.1039/d1dt02161c
Alexandre Poirot ₁ , Corinne Vanucci-Bacqué ₁ , Béatrice Delavaux-Nicot ₂ , Nadine Leygue ₁ , Nathalie Saffon-Merceron ₃ , Fabienne Alary ₄ , Florence Bedos-Belval ₁ , Eric Benoist ₁ , Suzanne Fery-Forgues ₁

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Strongly luminescent tricarbonylrhenium(I) complexes are promising candidates in the field of optical materials. In this study, three new complexes bearing a 3-(2-pyridyl)-1,2,4-triazole (pyta) bidentate ligand with an appended phenyl group were obtained in very good yields owing to an optimized synthetic procedure. The first member of this series, i.e. complex 1, was compared with the previously studied complex RePBO to understand the influence of the fluorescent benzoxazole unit grafted on the phenyl ring. Then, to gauge the effect of steric hindrance on the luminescence properties, the phenyl group of complex 1 was substituted in the para position by a bulky tert-butyl group or an adamantyl moiety, affording complexes 2 and 3, respectively. The results of theoretical calculations indicated that these complexes were quite similar from an electronic point of view, as evidenced by the electrochemical study. In dichloromethane solution, under excitation in the UV range, all the complexes emitted weak phosphorescence in the red region. In the solid state, they could be excited in the blue region of the visible spectrum and they emitted strong yellow light. The photoluminescence quantum yield was markedly increased with raising the size of the substituent, passing from 0.42 for 1 to 0.59 for 3. The latter complex also exhibited clear waveguiding properties, unprecedented for rhenium complexes. From this point of view, these easy-synthesized and spectroscopically attractive complexes constitute a new generation of emitters for use in imaging applications and functional materials. However, the comparison with RePBO showed that the presence of the benzoxazole group leads to unsurpassed mechanoresponsive luminescence (MRL) properties, due to the involvement of a unique photophysical mechanism that takes place only in this type of complex.

中文翻译：

苯基-pyta-三羰基铼(I)配合物：结合简化结构和空间位阻来调节光致发光性质

强发光的三羰基铼配合物是光学材料领域有希望的候选者。在这项研究中，由于优化的合成程序，以非常好的收率获得了带有 3-(2-吡啶基)-1,2,4-三唑 (pyta) 二齿配体和附加苯基的三种新配合物。该系列的第一个成员，即配合物1 ，与之前研究的配合物RePBO进行比较，以了解接枝在苯环上的荧光苯并恶唑单元的影响。然后，为了测量空间位阻对发光性质的影响，络合物1的苯基在对位被大的叔丁基或金刚烷基部分取代，分别得到络合物2和3 。理论计算结果表明，从电子角度来看，这些配合物非常相似，电化学研究证明了这一点。在二氯甲烷溶液中，在紫外范围激发下，所有配合物在红色区域发出微弱的磷光。在固态下，它们可以在可见光谱的蓝色区域被激发，并发出强烈的黄光。随着取代基尺寸的增加，光致发光量子产率显着增加，从1的0.42增加到3的0.59。后一种配合物还表现出清晰的波导特性，这对于铼配合物来说是前所未有的。从这个角度来看，这些易于合成且具有光谱吸引力的复合物构成了用于成像应用和功能材料的新一代发射体。然而，与RePBO的比较表明，苯并恶唑基团的存在导致了无与伦比的机械响应发光（MRL）特性，因为涉及仅在这种类型的复合物中发生的独特光物理机制。

更新日期：2021-09-15

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